Adsorbent matrix as propellant in aerosol package

ABSTRACT

Adsorbent materials adsorb large quantities of inert permanent gases and maintain the initial pressure inside aerosol packages throughout the useful life of the packages, thus acting as propellants.

FIELD OF THE INVENTION

The present invention generally relates to combinations of adsorbentmaterials and inert permanent gases, i.e., adsorbent matrices, that actas propellants in aerosol packages. More specifically, the adsorbentmaterial can be selected from the group comprising metal organicframework (MOF), covalent organic framework (COF), zeolitic imidazolateframework (ZIF), and combinations thereof, and the inert permanent gascan be selected from the group comprising nitrogen, carbon dioxide,helium, and argon. The adsorbent material adsorbs large quantities ofthe inert permanent gas and maintains the initial pressure inside theaerosol package throughout the useful life of the package.

BACKGROUND OF THE INVENTION

Aerosol dispensers have been in the market for a long period of time.They contain a propellant, which is typically a liquid at roomtemperature and elevated pressure, i.e., it is a liquified gas. Thus,the propellant maintains the initial pressure inside the dispenser untilall the liquid propellant is consumed, which typically happens at theend of life of the dispenser. Typical hydrocarbons in the early years ofaerosol dispensers were CFC-12 (dichlorodifluoromethane) and CFC-114(dichlorotetrafluoroethane), which were totally non-flammable. Then, inmid-1978, the U.S. government banned the use of CFC propellants becauseof their ability to deplete the stratospheric ozone. Then, the industrymoved to HCFC-22 (monochlorodifluoromethane) and HCFC-142b(1-chloro-1,1-difluoroethane), which had problems with slightflammability (HCFC-142b), mutagenicity (HCFC-22), and excessive internalpressure at 130° F. (180 psig limit by the DOT; HCFC-22). In about 1993,the U.S. EPA banned these two propellants because they determined that,like the CFCs, they cause depletion of the stratospheric ozone. In 1994,DuPont introduced the HFC-134a (1,1,1,2-tetrafluoroethane) as anon-flammable propellant, which however had excessive vapor pressure at130° F. (202 psig), and thus required specially-designed dispensers. Inaddition to those concerns, HFC-134a had a global warming potential(GWP) 1300 times as great as carbon dioxide (GWP of carbon dioxide=1). Afew years later, HFC-152a (1,1-difluoroethane) was introduced as apropellant with GWP 138. Also, HFC-152a is flammable. More recently,Honeywell (Fluorine Products Division) introduced HFO-1234ze(E)(trans-1,3,3,3,-tetrafluoroprop-1-ene; with reported GWP less than 1)and DuPont introduced HFO-1234yf (1,1,1,2,-tetrafluoroprop-1-ene). Othertypical propellants include propane, iso-butane, n-butane, dimethylether (DME), and their blends.

The use of inert permanent gases as propellants is hindered by the factthat inert permanent gases exhibit lower pressure in the dispenser asthe product is dispensed and the headspace increases. That decreasingpressure throughout the life of the aerosol product affects the aerosolqualities.

Accordingly, there is a need for a material that would allow inertpermanent gases to be used as propellants in aerosol products. Thatmaterial needs to adsorb large quantities of the inert permanent gas andrelease the appropriate amount of that gas very quickly when thepressure is reduced. The advantages of such a system are low costcompared to the latest propellants, low GWP (i.e., bettersustainability), non-flammability, and constant pressure throughout thelife of the aerosol product. Another advantage of such a system is theability to refill the aerosol package with the inert permanent gas aftereach emptying of the package and reuse it many times in the future(i.e., stronger support for the circular economy concept).

SUMMARY OF THE INVENTION

In one embodiment of the present invention, a method for generatingconstant pressure inside an aerosol package is presented. The methodcomprises the use of an adsorbent material and an inert permanent gas;wherein said inert permanent gas is adsorbed into said adsorbentmaterial to form an adsorbent matrix; wherein said adsorbent matrix hasan uptake constant K greater than about 0.015 g/g.psig at about 100psig; wherein said adsorbent matrix generates a pressure inside saidaerosol package; and wherein said pressure remains constant throughoutthe useful life of said aerosol package.

In another embodiment of the present invention, an aerosol package ispresented. The method comprises the use of an adsorbent material and aninert permanent gas; wherein said inert permanent gas is adsorbed intosaid adsorbent material to form an adsorbent matrix; wherein saidadsorbent matrix generates a final pressure ratio pressure; and whereinsaid final pressure ratio is greater than about 2.

In yet another embodiment of the present invention, an aerosol packageis presented. The aerosol package comprises a bag, a can, and a valve;wherein the volume between said bag filled with product and said can isa propellant volume; wherein said propellant volume comprises an MOF andcarbon dioxide; wherein said carbon dioxide is partly adsorbed in saidMOF, forming an adsorption matrix with uptake constant K greater thanabout 0.015 g/g.psig at about 100 psig, and the remainder of said carbondioxide is in equilibrium with said adsorbed carbon dioxide at apressure; and wherein said pressure remains constant throughout theuseful life of said aerosol package.

DETAILED DESCRIPTION OF THE INVENTION I Definitions

As used herein, the term “BET specific surface area” refers to aspecific surface area (i.e., surface area per unit mass) measured usingthe Brunauer—Emmett—Teller theory that describes the physical adsorptionof inert gas molecules on a solid surface and utilizes probing gases(e.g., nitrogen; that do not chemically react with the material surface)as adsorbates to quantify the specific surface area.

As used herein, the term “MOF” refers to Metal Organic Framework, whichis a material synthesized through the reaction of an organic componentand an inorganic component under controlled synthesis conditions (e.g.pH, solvent, temperature, concentrations) and using the solvent as thetemplate for the synthesis. MOFs are highly-ordered frameworks in whichthe metal ligand complexes form vertices that are connected by organiclinkers and often results in very high BET surface areas and pores ofmolecular dimensions.

As used herein, the term “COF” refers to Covalent Organic Framework,which is a material synthesized similar to MOF; however, in the COF alllinked groups are organic.

As used herein, the term “ZIF” refers to Zeolitic Imidazolate Framework,which is a special form of MOF in which the transition metal ions arelinked by substituted imidazolate ions and form frameworks with atopology of a known zeolite or zeolite-like.

As used herein, the term “constant” refers to a pressure varying by lessthan about 20% around a set pressure value.

As used herein, the term “permanent gas” refers to a gas which isgaseous under typical use conditions (e.g. temperature between about 0°C. and about 60° C., and pressure between about atmospheric and about200 psig).

As used herein, the term “inert permanent gas” refers to a permanent gaswhich does not negatively affect (either physically or chemically) thematerials which it comes in contact with.

As used herein, the term “adsorbent matrix” refers to the combination ofan adsorbent material and an inert permanent gas, which has adsorbedinto this adsorbent material.

As used herein, the term “final pressure ratio” refers to the ratio ofthe final pressure in the aerosol package in the presence of theadsorbent matrix and the final pressure in the aerosol package in theabsence of the adsorbent matrix.

As used herein, the term “uptake constant of the adsorbent matrix”refers to the the mass of the inert gas adsorbed in the adsorbentmateruial per unit mass of the adsorbent material and unit pressure, allmeasured at 25° C. The uptake constant of the adsorbent matrix is notedas K with units of (g gas)/(g adsorbent material).(psig) or simplyg/g.psig.

As used herein, the term “bag-in-bottle” refers to an aerosol packagecomprising a bag attached to a bottle, and a valve. The productformulation is placed in the bag, the propellant is placed in the spacebetween the bottle and the bag, and the propellant pushes the productthrough the valve when it is actuated.

As used herein, the term “bag-on-valve” refers to an aerosol packagecomprising a bag attached to a valve, whereas the bag is inside abottle. The product formulation is placed in the bag, the propellant isplaced in the space between the bottle and the bag, and the propellantpushes the product through the valve when it is actuated.

II Adsorbent Materials

Unexpectedly, it has been found that when MOF, COF, or ZIF materials areused as substrates for adsorption of inert permanent gases, theresulting adsorption matrices act as propellants to dispense products inaerosol form, i.e., generate a constant pressure inside the aerosolpackage. This constant pressure behavior is very similar to what typicalhydrocarbon propellants exhibit when they transition from liquid to gasphase. Contrary to that, in the absence of these MOF, COF, or ZIFmaterials, the pressure of the inert permanent gases is reduced everytime the consumer dispenses the product. This reduction in pressurethroughout the life of the package has negative impact on the quality ofthe aerosol.

In one embodiment of the present invention, the adsorbent material isselected from the group comprising MOF, COF, ZIF, or mixtures thereof.In another embodiment of the present invention, the adsorbent materialcomprises an MOF. In yet another embodiment of the present invention,the adsorbent material comprises a COF. In even yet another embodimentof the present invention, the adsorbent material comprises a ZIF.

The MOF materials are porous periodic materials which include cationicmetal-containing clusters (called secondary building units—SBU) linkedby anionic organic linkers (typically carboxylates). Non-limitingexamples of MOF materials are: MOF-5 [Zn₄O tetrahedral groups linked byterephthalate groups (1,4-benzenedicaroxylate (BDC)); Zn₄O(BDC)₃];MOF-177 [Zn₄O tetrahedral groups linked by benzene tri-benzoic acidgroups (BTB); Zn₄O(BTB)₃]; and MIL-101 [Cr₃F(H₂O)₂O(BDC)₃.nH₂O; n˜25;BDC=1,4-benzenedicarboxylate]. MOF-177 has a BET specific surface areabetween about 3,100 and about 4,630 m²/g, pore diameter of 1.06-1.27 nm,pore volume of 2.65 mL/g, and CO₂ uptake of about 35 mmol/g (1.54 g/g)at ambient temperature and 45 bar pressure (4.5 MPa or 652.7 psi). Atambient temperature, the CO₂ uptake of MOF-177 is 0.08 g/g at 1 bar (0.1MPa or 14.5 psi) and 0.4 g/g at 14 bar (1.4 MPa or 203 psi). MIL-101 hasa BET specific surface area of about 3,000 m2/g, mesopores of 2.9 and3.4 nm, pore volume of 1.8 mL/g, and CO₂ uptake of 0.74 g/g at 15 bar(1.5 MPa or 217.6 psi) and 1 g/g at 30 bar (3 MPa or 435.1 psi), both atambient temperature.

The COF materials are porous periodic materials which include allorganic linked groups. Non-limiting examples of COF materials are: COF-1[condensed benzene 1,4-diboronic acid]; and COF-5 [benzene diboronicacid linked to a trigonal hexahydroxy SBU].

Finally, the ZIF materials are special cases of the MOF materials inwhich the transition metal ions are linked by substituted imidazolateions and form frameworks that have topology either that of a knownzeolite or zeolite-like. Non-limiting examples of ZIF materials are:ZIF-11 [with a zeolite RHO topology]; and ZIF-20 [with a zeolite LTAtopology].

In one embodiment of the present invention, the MOF material comprisesMIL-101. In another embodiment of the present invention, the MOFmaterial comprises MOF-177.

In one embodiment of the present invention, the MOF material is in theform of powder. In another embodiment of the present invention, the MOFmaterial is in the form of particles. In yet another embodiment of thepresent invention, the MOF material is in the form of a membrane. Ineven yet another embodiment of the present invention, the MOF materialis in the form of a sheet.

In one embodiment of the present invention, the COF material is in theform of powder. In another embodiment of the present invention, the COFmaterial is in the form of particles. In yet another embodiment of thepresent invention, the COF material is in the form of a membrane. Ineven yet another embodiment of the present invention, the COF materialis in the form of a sheet.

In one embodiment of the present invention, the ZIF material is in theform of powder. In another embodiment of the present invention, ZIFmaterial is in the form of particles. In yet another embodiment of thepresent invention, the ZIF material is in the form of a membrane. Ineven yet another embodiment of the present invention, the ZIF materialis in the form of a sheet.

III Inert Permanent Gases

In one embodiment of the present invention, the inert permanent gas isselected from the group comprising nitrogen, carbon dioxide, helium,argon, air, moisture, and mixtures thereof. In another embodiment of thepresent invention, the inert permanent gas is selected from the groupcomprising nitrogen, carbon dioxide, helium, argon, and mixturesthereof. In yet another embodiment of the present invention, the inertpermanent gas comprises carbon dioxide.

In one embodiment of the present invention, the inert permanent gas isadsorbed into the adsorbent material to create an adsorbent matrix. Inanother embodiment of the present invention, the pressure of the inertpermanent gas is about 140 psig. In yet another embodiment of thepresent invention, the pressure of the inert permanent gas is about 140psig and remains constant throughout the useful life of the aerosolpackage.

In one embodiment of the present invention, the pressure of the inertpermanent gas is about 160 psig. In another embodiment of the presentinvention, the pressure of the inert permanent gas is about 160 psig andremains constant throughout the useful life of the aerosol package. Inyet another embodiment of the present invention, the pressure of theinert permanent gas is about 180 psig. In even yet another embodiment ofthe present invention, the pressure of the inert permanent gas is about180 psig and remains constant throughout the useful life of the aerosolpackage.

In one embodiment of the preset invention, the pressure of the inertpermanent gas is less than about 140 psig. In another embodiment of thepreset invention, the pressure of the inert permanent gas is less thanabout 160 psig. In yet another one embodiment of the preset invention,the pressure of the inert permanent gas is less than about 180 psig.

In one embodiment of the preset invention, the pressure of the inertpermanent gas is less than about 100 psig. In another embodiment of thepreset invention, the pressure of the inert permanent gas is less thanabout 80 psig. In yet another one embodiment of the preset invention,the pressure of the inert permanent gas is less than about 60 psig. Ineven yet another embodiment of the preset invention, the pressure of theinert permanent gas is less than about 40 psig.

IV Aerosol Packages

The aerosol packages comprise a bottle, a delivery device, and a valve.Optionally, the aerosol packages have a base cup, a label, a cap, and atrigger to improve the ergonomics of dispensing the aerosol product. Inone embodiment of the present invention, the aerosol package uses abag-on-valve (BOV) dispensing system. The system separates the productfrom the pressurizing agent with a bag attached to the valve.Preferably, the bag is hermetically sealed. The bag can be singlelayered or multi-layered laminate. The space between the bottle and thebag, where the adsorption matrix (i.e., adsorption material and inertpermanent gas) resides, is called the headspace.

The aerosol products of the present inventionare delivered from a totalpackage comprising a delivery device, a valve to control flow, and astable plastic package that holds the product when sealed using thevalve. The delivery device can be any known delivery device including,but not limited to, button actuator and a porous sintered dome.Likewise, any known valve can be used that is capable of sealing thepressurized product within the plastic package and being easily openedand closed to control the release of the product to the delivery device.Both the delivery device and valve can be made of any materialincluding, but not limited to, metal, plastic, or glass.

The uptake constant of the adsorbent matrix is noted as K with units of(g gas)/(g adsorbent material).(psig) or simply g/g.psig. The amount ofadsorbent material in the aerosol package is noted as M and the totalamount of the inert gas in the aerosol package is noted as m, and bothhave units of g. The initial pressure in the headspace of the aerosolpackage is noted as P₀ with units of psig; and the ratio of initialheadspace to final headspace is noted as λ, which is dimensionless.Then, the appropriate adsorbent matrix has an uptake constant K, wherein

$K \geq {\left( \frac{m}{{MP}_{0}} \right){\left( \frac{1 - {1.25\lambda}}{1 - \lambda} \right).}}$

In one embodiment of the present invention, the uptake constant of theadsorbent matrix is greater than about 0.015 g/g.psig at about 100 psigheadspace pressure (or equivalently, about 1.5 g/g at about 100 psig).In another embodiment of the present invention, the uptake constant ofthe adsorbent matrix is greater than about 0.02 g/g.psig at about 100psig headspace pressure (or equivalently, about 2 g/g at about 100psig). In yet another embodiment of the present invention, the uptakeconstant of the adsorbent matrix is greater than about 0.04 g/g.psig atabout 100 psig headspace pressure (or equivalently, about 4 g/g at about100 psig). In even yet another embodiment of the present invention, theuptake constant of the adsorbent matrix is greater than about 0.08g/g.psig at about 100 psig headspace pressure (or equivalently, about 8g/g at about 100 psig).

In one embodiment of the present invention, the final pressure ratio isgreater than about 2. In another embodiment of the present invention,the final pressure ratio is greater than about 2.5. In yet anotherembodiment of the present invention, the final pressure ratio is greaterthan about 3. In even yet another embodiment of the present invention,the final pressure ratio is greater than about 3.5.

V Examples

Example 1

An aerosol dispenser contains 300 mL of product in a bag and 100 mL ofan MOF and CO₂ in the space outside the bag (also called headspace). Theinitial pressure in the dispenser P₀ is 100 psig (0.79 MPa or 7.9 bar)and the headspace contains 10 g of the MOF (i.e., M=10 g). At thatpressure, the CO₂ uptake by the MOF is 2 g CO₂/g MOF (or equivalently,45.5 mmol CO₂/g MOF), and thus the MOF has an uptake constant K equal to0.02 g CO_(2/)g MOF.psig, and the total amount of CO₂ m is 21.4 g. Whenall the product is dispensed, the total headspace becomes 400 mL (i.e.,λ=0.25) and the final pressure inside the dispenser becomes about 84psig. If there is not any MOF in the headspace of the dispenser, thefinal CO₂ pressure would be about 25 psig. Thus, the final pressureratio in the aerosol package is 84/25=3.36.

The foregoing description is given for clearness of understanding only,and no unnecessary limitations should be understood therefrom, asmodifications within the scope of the invention may be apparent to thosehaving ordinary skill in the art.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

Every document cited herein, comprising any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. An aerosol package comprising a bag, a can, and avalve; wherein the volume between said bag filled with product and saidcan is a propellant volume; wherein said propellant volume comprises anMOF and carbon dioxide; wherein said carbon dioxide is partly adsorbedin said MOF, forming an adsorption matrix with uptake constant K greaterthan about 0.015 g/g.psig at about 100 psig, and the remainder of saidcarbon dioxide is in equilibrium with said adsorbed carbon dioxide at apressure; and wherein said pressure remains constant throughout theuseful life of said aerosol package.
 2. The method of claim 1, whereinsaid MOF is MIL-101.
 3. The method of claim 1, wherein said MOF isMOF-177.
 4. The method of claim 1, wherein said pressure inside saidaerosol package is about 100 psig.-10.
 5. The method of claim 1, whereinsaid aerosol package is selected from the group comprising abag-in-bottle package and a bag-on-valve package.
 6. The method of claim5, wherein said aerosol package is a bag-on-valve package; wherein saidadsorbent material is MIL-101; and wherein said pressure is about 100psig.